Surfactants

ABSTRACT

Compounds of the formula R 2 .[(AO) n .R 3 ] m , where R 2  is a residue of a group having at least m active hydrogen atoms derived from hydroxyl and/or amino and/or amido groups, AO is alkyleneoxy, n is 2 to 200; R 3  includes residue(s) of alkenyl succinic acids and optionally other acids, and m is 2 to 10, but when m is 2 there are other restrictions in the definitions, are disclosed as useful thickeners and/or dispersants in aqueous systems. The use of such materials as thickeners is also disclosed.

[0001] This invention relates to derivatives of substituted succinicacids and to the use of such derivatives particularly as thickenersespecially in personal care compositions, especially such compositionsincluding large proportions of other surfactants, especially detergentsurfactants as for example used in shampoos, particularly baby shampoos.

[0002] Some derivatives of substituted succinic acids are described inEP 0107199 B as useful surfactants under acid conditions and publishedPCT Application No WO 94/00508 A describes surfactants based onalk(en)yl substituted succinic acid alkylene oxide esters and amides.Subsequently published PCT Applications describe the use of groups ofthis class of surfactant in various end use applications: in WO 95/06070A as emulsifiers in oil in water emulsion polymerisation, in WO 95/06096A as detergents in so-called hard surface cleaning, in WO 95122896 A asemulsifiers in agrochemical formulations and in WO 95/22897 A asadjuvants in agrochemical formulations.

[0003] We have now found that esters of alkyl or alkenyl succinic acidswith polyalkylene oxide derivatives of polyhydroxyl compounds in whichthere are two or more and especially three or more ester groupsincluding alkenyl succinic acid ester groups, in particular where thereare three or more alkyl or alkenyl succinic acid ester groups, can havevery useful thickening and or dispersant properties.

[0004] This invention accordingly provides compounds of the formula (1):

R².[(AO)_(n).R³]_(m)   (1)

[0005] where:

[0006] R² is the residue of a group having at least m active hydrogenatoms derived from hydroxyl and/or amino and/or amido groups;

[0007] AO is an alkylene oxide residue, which may vary along the chain;

[0008] each n is from 2 to 200;

[0009] m is from 2 to 10; and

[0010] each R³ is H, hydrocarbyl, particularly a C₁ to C₂₂ alkyl oralkenyl, a long chain alk(en)yl succinic acyl group of the formulaOC.(HR)C.C(HR¹).COY where:

[0011] one of R and R¹ in the succinic moiety is C₈ to C₂₂ alkenyl oralkyl and the other is hydrogen, and

[0012] Y is a group OM where M is hydrogen, metal, amonium, amine,especially alkylamine (including alkanolamine), onium, hydrocarbyl,desirably C₁ to C₂₂ hydrocarbyl, more particularly alkyl, especially C₁to C₂₂ alkyl; or

[0013] Y is NR⁴R⁵ where R⁴ and R⁵ are each independently hydrogen,hydrocarbyl, particularly alkyl, including substituted hydrocarbyl suchas substituted alkyl, particularly hydroxyl substituted hydrocarbyl,especially polyhydroxy hydrocarbyl, such as hydroxyl substituted andespecially polyhydroxy substituted alkyl;

[0014] or a long chain acyl group —OC.R⁶, where R⁶ is a long chainhydrocarbyl group, particularly a C₈ to C₂₂ alkyl or alkenyl group;

[0015] or a short chain acyl group —OC.R⁷, where R⁷ is a short chainhydrocarbyl group, particularly a C₁ to C₇ alkyl or alkenyl group;

[0016] where at least two, and desirably at least three, of the groupsR³ are long chain acyl groups, and at least one, desirably at least twoand particularly at least three, of the long chain acyl groups is/arelong chain alkenyl or alkyl succinic group(s);

[0017] provided that where R¹ is ethylene glycolyl or propyleneglycolyl, m is 2, and both groups R² are alk(en)yl succinic groups, thetotal of the indices n is at least 120.

[0018] In particular, the invention provides compounds of the formula(1a):

R².[(AO)_(n).R³]m   (1a)

[0019] where:

[0020] R² is the residue of a group having at least m active hydrogenatoms derived from hydroxyl and/or amino and/or amido groups;

[0021] AO represents ethylene oxide residues or a mixture of ethyleneoxide residues and propylene oxide residues in which the molarproportion of ethylene oxide residues is at least 50% and desirably atleast 70%;

[0022] each n is from 10 to 200 such that the total of the indices n isat least 120

[0023] m is from 2 to 10;

[0024] each R³ is H; hydrocarbyl; particularly C₁ to C₂₂ hydrocarbyl,more particularly C₁ to C₂₂ alkyl or alkenyl;

[0025] a long chain alk(en)yl succinic acyl group of the formula:

—OC.(HR)C.C(HR¹).COY

[0026] where:

[0027] one of R and R¹ in the succinic moiety is C₈ to C₂₂ alkenyl oralkyl and the other is hydrogen, and

[0028] Y is a group OM where M is hydrogen, metal, amonium, amineespecially alkylamine (including alkanolamines), or Y is NR⁴R⁵ where R⁴and R⁵ are each independently hydrogen, a hydrocarbyl, particularlyalkyl, group, including substituted hydrocarbyl such as substitutedalkyl, particularly hydroxyl substituted hydrocarbyl, especiallypolyhydroxy hydrocarbyl, such as hydroxyl substituted and especiallypolyhydroxy substituted alkyl, groups;

[0029] a long chain acyl group —OC.R⁶, where R⁶ is a long chainhydrocarbyl group, particularly a C₈ to C₂₂ alkyl or alkenyl group; or

[0030] a short chain acyl group —OC.R⁷, where R⁷ is a short chainhydrocarbyl group, particularly a C₁ to C₇ alkyl or alkenyl group;

[0031] where at least two, and desirably at least three, of the groupsR³ are long chain acyl groups, and at least one, desirably at least twoand particularly at least three, of the long chain acyl groups is/arelong chain alkenyl or alkyl succinic group(s).

[0032] In addition to the compounds of the invention themselves, we havefound that related compounds (including some compounds falling withinthe definitions in our earlier WO 94/00508 A) can also successfully beused as thickeners. Accordingly, the invention includes, the use asthickeners, of compounds of the formula (II):

R¹².[(AO²)_(n2).R¹³]_(m2)   (II)

[0033] where:

[0034] R¹² is the residue of an optionally substituted hydrocarbyl grouphaving at least m active hydrogen atoms derived from hydroxyl and/oramino and/or amido groups;

[0035] AO² is an alkylene oxide residue, which may vary along the chain;

[0036] each n2 is from 10 to 200, such that the total of the indices n2is at least 50;

[0037] m2 is from 2 to 10; and

[0038] each R¹³ is H, hydrocarbyl, particularly a C₁ to C₂₂ alkyl oralkenyl,

[0039] a long chain alk(en)yl succinic acyl group of the formula:

—OC.(HR¹⁰)C.C(HR¹¹).COY²

[0040] where:

[0041] one of R¹⁰ and R¹¹ in the succinic acid moiety is C₈ to C₂₂alkenyl or alkyl and the other is hydrogen, and

[0042] Y² is a group OM² where M² is hydrogen, metal, amonium, amineespecially alkylamine (including alkanolamines) alkyl, especially C₁ toC₂₂ alkyl; or

[0043] Y² is NR¹⁴R¹⁵ where R¹⁵ and R¹⁵ are each independently hydrogen,a hydrocarbyl, particularly alkyl group, including substitutedhydrocarbyl such as substituted alkyl, particularly hydroxyl substitutedhydrocarbyl, especially polyhydroxy hydrocarbyl, such as hydroxylsubstituted and especially polyhydroxy substituted alkyl, groups;

[0044] or a long chain acyl group —OC.R¹⁶, where R¹⁶ is a long chainhydrocarbyl group, particularly a C₈ to C₂₂ alkyl or alkenyl group;

[0045] or a short chain acyl group —OC.R¹⁷, where R¹⁷ is a short chainhydrocarbyl group, particularly a C₈ to C₇ alkyl or alkenyl group;

[0046] where at least two of the groups R¹³ are long chain acyl groups,and at least one of the long chain acyl groups is a long chain alkenylor alkyl succinic group.

[0047] The compounds of and used in the invention have shown promise asthickeners in various systems, particularly those involving aqueousphases, mainly but not exclusively aqueous continuous phases. Theinvention accordingly includes the use of the compounds of the formula(I) as defined above as thickeners, in particular as thickeners inoil-in-water and water-in-oil emulsions, aqueous solutions anddispersions of solids in aqueous systems and as emulsifiers, especiallyas co-emulsifiers or emulsion stabilisers in combination with othersurfactants. In particular, in this aspect the invention specificallyincludes, the use as thickeners, of compounds of the formula (1a) asdefined above. The invention further includes oil-in-water andwater-in-oil emulsions, aqueous solutions and dispersions of solids inaqueous systems and which include at least one compound of the formula(I) as defined above as a thickener. In particular, in this aspect theinvention specifically includes, oil-in-water and water-in-oilemulsions, aqueous solutions and dispersions of solids in aqueoussystems and which include at least one compound of the formula (1a) asdefined above in an amount to provide effective thickening of thesystem.

[0048] The compounds of and used in the invention are particularlyuseful in the thickening of aqueous systems containing other surfactantsas in cleaning products especially shampoos and similar products.Conventional shampoos, particularly mild shampoos such as baby shampoos,thickened with conventional thickeners, particularly polyethylene glycol(PEG) distearates e.g. PEG 6000 distearate, tend to show near Newtonianflow behavior, in particular they are not substantially shear thinning.In consequence, the shampoos are made to heave relatively lowviscosities, and are thus difficult to handle, so that they will notexhibit the ‘gel-ball’ effect when rubbed between the hands. In thisinvention, the thickeners show significant shear thinning and thisenables shampoo formulations to be made having higher viscosity, so thatit is easier to handle, but that do not ‘ball up’ when rubbed in thehands or hair because they are shear thinning.

[0049] The compounds of and used in the invention have shown promise asdispersants in various systems, particularly those involving dispersionof solids in aqueous phases. The invention accordingly includes the useof the compounds of the formula (I) as defined above as dispersants,particularly as dispersants for solids in aqueous phases, especiallypigment solids in aqueous phases. The invention further includesdispersions of solids in aqueous systems which include at least onecompound of the formula (I) as defined above as a dispersant. Inparticular, in this aspect the invention specifically includes aqueousdispersions of solids which include at least one compound of the formula(Ia) as defined above in an amount to provide effective dispersion ofthe solid in the aqueous phase.

[0050] Among the uses within the invention, the invention specificallyincludes oil-in-water and water-in-oil emulsions, aqueous solutions anddispersions of solids in aqueous systems and which include at least onecompound of the formula (II) (including compounds of the formula (I) orformula (Ia)) as defined above as a thickener.

[0051] The compounds of and used in the invention are at leastnotionally built up from the group R² or R¹² which can be considered asthe “core group” of the compounds. This core group is the residue (afterremoval of m active hydrogen atoms) of a compound containing at least mactive hydrogen atoms in hydroxyl and/or amino and/or amido groups.Usually it is the residue of an optionally substituted hydrocarbylgroup, particularly a C₃ to C₃₀ hydrocarbyl compound. At its simplestthe core group can be an ethylene glycolyl (—O.C₂H₄.O—) or propyleneglycolyl (—O.C₃H₆.O—) group, in which case, when the group AO (or AO²)is an ethyleneoxy or propyleneoxy group, the core group can (notionally)be considered as being any of the ethylene or propylene glycolyl groupsalong the chain. For convenience, the (or a) group near the middle ofthe chain will be considered as being the core group in this case and inthis case (when further both end acyl groups are substituted succinicgroups), among the compounds of the invention the total number ofethyleneoxy and propyleneoxy groups is at least 120, although the numbercan be lower than this in the method and use of the invention. However,the core group will often be a residue where at least 3 active hydrogenatoms have been removed.

[0052] Examples of core groups include the residues of the followingpounds after removal of at least two active hydrogen atoms:

[0053] 1 glycerol and the polyglycerols, especially diglycerol andtriglycerol;

[0054] 2 tri- and higher polymethylol alkanes such as trimethylolethane, trimethylol propane and penterythritol;

[0055] 3 sugars, particularly non-reducing sugars such as sorbitol andmannitol, etherified derivatives of sugars such as sorbitan (the cyclicdehydro-ethers of sorbitol), partial alkyl ethers of sugars such asmethyl glucose and alkyl (poly-)saccharides, and ether oligo-/poly-mersof sugars such as dextrins, esterified derivatives of sugars such asfatty acid esters such as the fatty acid e.g. lauric, palmitic, oleic,stearic and behenic acid, esters of sorbitan and the sorbitols(themselves well known as surfactants and which when alkoxylkated withethylene oxide form the well known polysorbate group of surfactants inwhich at least part of the ethoxylation is effectively inserted betweenthe fatty acid residue and the sorbitol residue), (non-reducing sugarsbeing preferred over reducing sugars as they are more stable undertypical synthetic conditions and tend to give products which are lesssusceptible to oxidation and are less highly coloured—colour mainlyarising from oxidative degradation);

[0056] 4 polyhydroxy carboxylic acids especially citric and tartaricacids;

[0057] 5 amines including di- and poly-functional amines, particularlyalkylamines including alkyl diamines such as ethylene diamine(1,2-diaminoethane);

[0058] 6 amino-alcohols, particularly the ethanolamines, 2-aminoethanol,di-ethanoiamine and triethanolamine;

[0059] 7 carboxylic acid amides such as urea, malonamide andsuccinamide; and

[0060] 8 amido carboxylic acids such as succinamic acid.

[0061] The index m is a measure of the functionality of the core groupand generally the alkoxylation reactions will replace all activehydrogen atoms in the molecule from which the core group is derived. (Ofcourse, reaction at a particular site may be inhibited by suitableprotection.) The terminating hydroxyl groups of the polyalkylene oxidechains in the resulting compounds are then available for reaction withacyl compounds to form ester linkages and other compounds (if desired)(see below). The index m will typically be in the range 2 to 10, moreusually from 2 and especially 3 to 6.

[0062] The alkylene oxide groups AO and AO² are typically groups of theformula: —(C_(m)H_(2m)O)— where m is 2, 3 or 4, desirably 2 or 3, i.e.an ethyleneoxy (—C₂H₄O) or propyleneoxy (C₃H₆O—) group, and it mayrepresent different groups down the alkylene oxide chain. Generally, itis desirable that the chain is a homopolymeric ethylene oxide chain.However, the chain may be a homopolymer chain of propylene glycolresidues or a block or random copolymer chain containing both ethyleneglycol and propylene glycol residues. Usually, where co-polymeric chainsof ethylene and propylene oxide units are used the molar proportion ofethylene oxide units used will be at least 50% and more usually at least70%.

[0063] For thickener applications, especially in aqueous systems, thenumber of alkylene oxide residues in the polyalkylene oxide chains, i.e.the value of the each parameter n. and n2, will generally be from 15 to150, particularly 20 to 120, especially 50 to 100. In practice, incompounds of and used in this invention the total degree of alkoxylationmay be a useful guide to satisfactory thickener properties. Thus,desirable compounds include those where the total of the indices n isfrom 30 to 300, particularly 50 to 250, especially 80 to 200.

[0064] For dispersant applications, especially the dispersion of solidssuch as pigments in aqueous systems, the number of alkylene oxideresidues in the polyalkylene oxide chains, i.e. the value of the eachparameter n and n2, will generally be from 10 to 100, particularly 20 to80, especially 40 to 70. The total degree of alkoxylation (the total ofall the indices n and n2) will typically be from 30 to 300, particularly50 to 250, especially 80 to 200.

[0065] In any particular product, the value of the index n or n2 is anaverage value which includes statistical variation in the chain lengthbetween the same substituent in different molecules and betweendifferent substituent groups. For use as thickeners in mainly aqueoussystems, the compounds of and used in the invention desirably have amolecular weight of at least 4000 D and typically not more than about8000 D. For use as dispersants, the molecular weight will typically befrom 1000 to 4000 D.

[0066] The groups R³ and R¹³ are the “terminating groups” of thepolyalkylene oxide chains. For practical thickener use at least two ofthe terminating groups will be acyl groups and desirably at least two ofthe terminating groups are alk(en)yl succinic groups as defined above informuale (I), (Ia) or (II). Where R³ and R¹³ are alk(en)yl succinicgroups as defined above the one of R and R¹ which is a C₈ to C₂₂ alkylor alkenyl group is particularly a C₁₆ or longer group. For dispersantuse, generally at least two of the terminating groups are alk(en)ylsuccinic groups as defined above in formuale (I), (Ia) or (II). Where R³and R¹³ are alk(en)yl succinic groups as defined above the one of R andR¹ which is a C₁₂ to C₁₈ alkyl or alkenyl group is particularly a C₁₂ toC₁₈ group.

[0067] The number of terminating groups may exceed the number of acylgroups and in this case, the remaining terminating groups can behydrogen atoms or hydrocarbyl, particularly alkyl, groups. Further,within alk(en)yl succinic terminating groups as defined above informuale (I), (Ia) or (II) the groups Y and Y² may be hydrocarbyl,particularly alkyl, groups. Suitable such hydrocarbyl groups includelower alkyl groups, e.g. C₁ to C₆ alkyl groups such as methyl or ethylgroups, acting as chain end caps for one or more of the polyalkyleneoxide chains mainly to alter the degree of hydrophilicity of thecompounds, and longer chain alkyl or alkenyl groups e.g. C₈ to C₂₂ andparticularly C₁₆ or longer, alkyl or alkenyl groups such as lauryl,oleyl and stearyl groups or mixed alk(en)yl groups derived from naturalfats or oils or from distillation cuts in petrochemical synthesis,acting as secondary hydrophobe(s) in the molecule.

[0068] It can be desirable to avoid the presence of free (unreacted)anhydride in compounds of and used in the invention, especially wherethe intended use of the compounds is in personal care applications. Inview of the ease of carrying out the esterification reaction with theanhydrides, residual free anhydride is likely only where the nominalproduct has no remaining available reactive hydrogens. A convenient wayto do this, especially on the small scale, is to use slightly less thanthe stoichiometric proportion of anhydride corresponding to completereaction. This is particularly useful where the number of succinic esterfunctions in the target molecule is 3 or more. (This can be seen in someof the Examples below.) On the laboratory scale, the ‘shortfall’ ofanhydride will typically be no less than about 5% (molar) and typicallyabout 1 to 3% (molar). In industrial scale production, it is usuallyeasier to drive the reaction more nearly to stoichiometric balance andthe ‘shortfall’ may not be required or will typically be less than about1% (molar).

[0069] Where for the groups R³ the number of acyl residues in themolecule is significantly less than m, the distribution of such groupsmay depend on the nature of the core group and on the extent and effectof the alkoxylation of the core group. Thus, where the core group isderived from pentaerythritol, alkloxylation of the core residue willtypically be evenly distributed over the four available sites from whichan active hydrogen can be removed and on esterification of the terminalhydroxyl functions the distribution of acyl groups will be close to theexpected random distribution. However, where the core group is derivedfrom compounds, such as sorbitol or sorbitan, where the active hydrogenatoms are not equivalent, alkoxylation will typically give unequal chainlengths for the polyalkyleneoxy chains. This may result in some chainsbeing so short that the other (longer) chains exert significant stericeffects making esterification at the “short chain” terminal hydroxylgroups relatively difficult. Esterification then will generallypreferentially take place at the “long chain” terminal hydroxyl groups.The end result will be a statistical distribution that is not at firstsight “random.”

[0070] The groups Y and Y² may also be amido groups NR⁴R⁵ or NR¹⁴R¹⁵ inwhich the substituent groups can be hydrogen, a hydrocarbyl,particularly alkyl group, including substituted hydrocarbyl such assubstituted alkyl, particularly hydroxyl substituted hydrocarbyl,especially polyhydroxy hydrocarbyl, such as hydroxyl substituted andespecially polyhydroxy substituted alkyl, groups. When one or both ofthese groups is(are) alkyl it(they) can be lower alkyl groups, e.g. C₁to C₆ alkyl groups such as methyl or ethyl groups, or longer chain alkyle.g. C₈ to C₂₂ groups such as lauryl, oleyl and stearyl groups or mixedalkyl groups derived from natural fats or oils or from distillation cutsin petrochemical synthesis, acting as secondary hydrophobe(s) in themolecule.

[0071] Where one or more of these substuents is a polyhydroxysubstituted hydrocarbyl it is particularly a polyhydroxy alkyl groupdesirably having a linear carbon chain of from 4 to 7 carbon atoms andat least three hydroxyl groups directly bonded to chain carbon atoms.The group may include substituents, in particular, alkoxy groups e.g. byetherification of further hydroxyl groups or polyalkylene oxide chains,but the group desirably includes at least three free hydroxyl groupsincluding such hydroxyl groups on substituents of the basic chain.Particularly the group is an open chain tetratol, pentitol, hexitol orheptitol group or an anhydro derivative of such a group. Especiallydesirably, the group is the residue of, or a residue derived from, areducing sugar, particularly a monosaccharide such as glucose orfructose, a disaccharide such as maltose or palitose or a higheroligosaccharide. Where the group is the residue of, or a residue derivedfrom, a monosaccharide, the saccharide derived group or residue willusually be present as an open chain material. When present such as groupwill form a secondary hydrophile and as such it will usually bedesirable that the hydrophilicity of this group is not unduly reduced.The open chain form of such groups is typically the most hydrophilicform and will thus usually be the form desired. Groups includinginternal cyclic ether functionality can however be used, if desired, andmay be obtained inadvertently if the synthetic route exposes the groupto relatively high temperatures or other conditions which promoteetherification. Where this group is the residue of, or a residue derivedfrom, an oligosaccharide it can be considered as an open chainmono-saccharide derived group or residue with a saccharide oroligosaccharide substituent. Particularly useful such groups are derivedfrom glycoses and are of the formula: —CH₂.(CHOH)₄CH₂OH, e.g.corresponding to residues from glucose, mannose or galactose. In thiscase the amido group is conveniently called a glycamine group and thecorresponding amides can be called glycamides. Most commonly such agroup will be derived from glucose and the corresponding amine andamides are called glucamines and glucamides. As with the amido groupsdescribed above any unsubstituted hydrocarbyl group is particularly ashort or long chain alkyl group.

[0072] Among the compounds of the invention, those where the alk(en)ylgroup R/R¹ is a C₈ to C₁₈ alkenyl or alkyl group are particularlyuseful. Generally in use a thickeners in oil-in-water dispersions oremulsions, compounds where R/R¹ is a C₁₂ and especially C₁₄ to C₁₈alkenyl or alkyl group are especially desirable. Similarly, compoundswhere the group R or R¹ is an alkenyl group are more desirable thanthose where the group is alkyl. Compounds where the group R or R¹ is analkenyl group, particularly a C₈ to C₂₂ alkenyl group and especially aC₁₄ to C₂₀ alkenyl group, form a specific aspect of the invention.

[0073] The compounds of the invention can be made by reacting analkoxylated polyhydric alcohol of the formula: R².[(AO)_(n).H]_(m) whereR², AO, n and m are as defined above, with an alk(en)yl succinicanhydride, and, optionally, a reactive derivative of a fatty acid of theformula H₂OC.R⁶, where R⁶ is as defined above, in molar ratioscorresponding to the number of ASA and optional fatty acid residuesdesired in the product.

[0074] Reactions between the alk(en)yl succinic anhydride and theprecursor hydroxylic reagent can readily be carried out, with or withoutcatalysts, by bringing the hydroxylic reagent into contact with thealk(en)yl succinic anhydride. Reaction occurs typically, at temperaturesbelow 200° C. and even below 100° C. The reactants will usually be usedin at least approximately stoichiometric proportions. Particularly wherestoichiometric proportions are used, further purification does notusually appear to be necessary, but can be carried out if desired.

[0075] Where an acyl residue is included in the molecule it will usuallybe introduced by reaction between an appropriate hydroxylic precursorand the corresponding acid or a reactive derivative such as an acylhalide, especially chloride, ester with a short chain alcohol such asmethanol or ethanol, or a mixed anhydride, the other acyl reside beingof a relatively volatile acid such as acetic acid. The direct reactionbetween the fatty acid and the hydroxylic precursor can be carried out,with or without catalysts, by heating typically to a temperature ofgreater than 100° C. Synthesis using reactive derivatives will usuallybe possible under milder conditions.

[0076] The products of the invention are typically a mixture of isomerscorresponding to the two senses of the alk(en)yl succinic anhydride ringopening during synthesis. We have noted that the alkenyl or alkyl chainseems to have a minor steric effect on the isomer ratio with the isomerratio being typically about 60:40, the major isomer arising fromnucleophilic attack at the anhydride carbonyl group remote from thealkenyl or alkyl group (probably because of steric hindrance).

[0077] The alkenyl succinic anhydride precursors may be produced byreacting maleic anhydride with an olefin having 6 to 22, particularly 8to 18, carbon atoms, preferably with an excess, for example a 50 to 200%excess, of olefin at a temperature in the range 150 to 400° C. andpreferably 180 to 250° C. and removing excess olefin for example bydistillation which is suitably carried out under vacuum. No catalyst isnecessary, but it is preferred than an antioxidant is present. Theseanhydrides are well known commercial materials. In alkenyl succinicanhydrides prepared as described above the double bond normally lies inthe 2-position in the alkenyl substituent.

[0078] To make products where the group R or R¹ is an alkyl group theneither the unsaturated products can be hydrogenated or, and preferably,the intermediate alkenyl succinic anhydride can be hydrogenated to givean alkyl succinic anhydride. Typically, hydrogenation of the anhydrideis carried out over a hydrogenation catalyst such as Raney nickel or aPd/C catalyst. Temperatures of from 15 to 100° C. and pressures of up to200 bar absolute may be used and, if desired a solvent may be present.For example, the hydrogenation reaction on an alkenyl succinic anhydridemay be carried out on the neat liquid at 60° C. at 5 bar H₂ pressureusing 5% w/w of Pd/C catalyst over a period of for example about 6hours.

[0079] The alkoxylates used in the synthesis can be made by conventionalroutes. For most simple alkoxylates and polysorbate type compounds theseare well known. However, some of the compounds generating the coregroups may not be directly alkoxylated as desired. For example, thedirect synthesis of a polyethoxylate of pentaerythritol and ethyleneoxide is not practical as the pentaerythritol would need to be heated toabove 200° C. to melt it and direct ethoxylation at such temperatures isdangerous! This problem can be sidestepped by ethoxylation in a suitablesolvent, such as dimethyl glyoxime, or (and particularly if it isdesired to avoid solvents) pentaerythritol can first be propoxylated (atabout 200° C. under conventional base catalysed conditions) to add about1 mole of oxypropylene residues per mole of hydroxyl in thepentaerythritol (in practice typically about 3 to 3.5 moles of propyleneoxide are added per mole of pentaerythritol). This moderatelypropoxylated material is typically a liquid at ambient temperature or atsuperambient temperatures (up to about 150° C. and typically at about130° C.) and can then be ethoxylated conventionally. Where the overalldegree of ethoxylation is above about 10 oxyethylene residues per moleof pentaerythritol the effect of the initial propoxylation does notalter the properties of the product significantly.

[0080] Other approaches to this problem include the use of solvents ordiluents as carriers for the material to be alkoxylated. Suitablesolvents are inert to the alkoxylation conditions and remain liquid atprocess temperatures and include materials such as dimethyl glyoxime(diglyme). In industrial scale batch production, a portion (‘heel’) ofthe previous batch may be retained as the solvent/diluent for the rawmaterial in the next batch. Commonly, in a sequence of batch operations,the first batch uses a solvent, and subsequent batches use a heel fromthe previous batch so that the need to remove the solvent from theproduct rapidly diminishes. Similarly in continuous processes,particularly where reagents are continuously fed to a reaction vesselholding a relatively large amount of reagents and products, and fromwhich product is continuously withdrawn, the process may be started upusing a solvent (often at much less than the rated full capacity of theequipment) and the reaction mix then used as solvent for further rawmaterials.

[0081] Compounds according to the invention have dispersant and/orthickening capabilities. These properties make the compounds of theinvention suitable for use as surfactants in dispersing pigments andsimilar solids in aqueous media, and in thickening dispersions and/orsolutions and/or emulsions.

[0082] The compounds of this invention can be used as thickeners in awide variety of systems, particularly aqueous systems. Such applicationinclude use as thickeners in emulsion systems of the oil-in-water types.Examples include personal care applications in shampoos, liquid soap andcleanser products and toiletry applications. Accordingly, the inventionincludes the use of at least one compound of this invention as athickener in emulsions, especially aqueous oil-in-water and water-in-oiland oil-in-water emulsion systems. The amount of surfactant used in suchdispersant applications depends on the materials employed and theconcentration of the emulsion required, but will usually be in the range0.2 to 10%, more usually 0.05 to 5% and particularly 0.1 to 2.5% byweight of the disperse phase of the emulsion. Other end use applicationsinclude thickening surfactant formulations. Previously, such systemshave been thickened using amine oxide thickeners and replacements havebeen sought in order to remove any possibility of in situ formation ofnitrosamines. The compounds of and used in this invention can be madecontaining no nitrogen and thus eliminate any risk of nitrosamineformation from this source. Even where the compounds of the inventioninclude nitrogen, it is usually as amide groups which are not readilysusceptible to conversion into nitrosamine groups.

[0083] The following Examples illustrate the invention including themanufacture and properties of the compounds of the invention and theirend uses and the method of the invention. All parts and percentages areby weight unless otherwise specified.

[0084] Abbreviations (for compounds supplying core residues): PEpentaerythritol Tri-gly triglycerol eth diam ethylene diamine

[0085] In compounds made in the Synthesis Examples, where the number ofester groups is non integral, the product compounds are described asx(non-integral)-(alkenyl succinic acid)esters.

[0086] Materials Tween 20 polysorbate 20 Miranol C2M aqueous disodiumcocoamphoiacetate, 38% active Steol CS-330 aqueous sodium laurethsulfate, 29.1% active Dowci1200 quaternium-15 SLES sodium lauryl ethersulphate CDMO N,N-dimethyl-cocoylamine oxide PEG distearate Kessco brandpolyethylene glycol (PEG) 6000 distearate ester ex Stepan TR92 TR92grade titanium dioxide ex Tioxide Ltd Arlatone 1489 aqueous solution ofsodium cocyl isethionate and decyl glucoside surfactants ex ICISurfactants Tensiomild HM disodium laureth sulphosuccinate ex HicksonManro Tengobetain L7 cocamidopropyl betaine ex Goldschmidt Germaben IIPreservative ex Sutton Laboratories G 1821 PEG 6000 distearate ester exICI Surfactants Crothix proprietary thickener ‘pentaerythritolethoxylate tetrastearate’ ex Croda

[0087] Hydroxyl values were measured by the general method of ISO 4327and results are quoted as mg (KOH equivalent).g (product tested)⁻¹.

[0088] General viscosity measurements were made using Brookfliedviscometers of the type and operated as described in the respectiveExamples.

SYNTHESIS EXAMPLES SE1 to SE38

[0089] SE1—Di-(dodecenylsuccinic)ester of pentaerythritol 48-ethoxylatePentaerythritol 48-ethoxylate

[0090] A slurry of pentaerythritol (175 g; 1.28 mol) in dimethylglyoxime(diglyme—inert reaction diluent; 328 g) was placed in a 11 autoclave,potassium methoxide (1.24 g) added and the reaction mix vacuum deaeratedat 20° C. and vacuum stripped at 80° C. The mixture was heated to 125°C., propylene oxide (246.3 g; 4.25 mol) was added over about 1.5 hoursand the mixture allowed to reactat 125° C. overnight. The mixture wasthen vacuum stripped at 80° C. for 15 minutes to remove unreactedpropylene oxide, transferred to a glass distillation flask and thediglyme removed by vacuum distillation at 100° C. The product was 423.3g (ca 100% of theory) of pentaerythritol condensed with ca 3.3 propyleneoxide units (pentaerythritol 3.3 PO).

[0091] Pentaerythritol 3.3 PO (480.5 g; 1.46 mol) and potassiumhydroxide (5.22 g of a 45% by weight aqueous solution; 2.35 g) werecharged to a 21 autoclave, vacuum deaerated and dried by heating at 110°C. for 1 hour at 0.5 bara (250 kPa absolute) while sparging with drynitrogen gas. The reaction mix was heated to 135° C. and reacted withgaseous ethylene oxide (1025 g; 23.3 mol) fed gradually to theautoclave. At the end of the reaction, 990.7 g of the product weredischarged and neutralised with glacial acetic acid. This product had ahydroxyl value of 218.6 mg(KOH).g⁻¹ giving an average molecular weightof ca. 1027 corresponding approximately to pentaerythritol 3.3PO+16EO.Potassium hydroxide (2.34 g) were added to the product remaining in theautoclave (by calculation 514.8 g; 0.5 mol), the reaction mix dried asdescribed above and reacted as described above with further ethyleneoxide (701 g; 15.9 mol). A portion (913.6 g) of this product wasdischarged and neutralised with glacial acetic acid. This product had ahydroxyl value of 93.1 mg(KOH).g⁻¹ giving an average molecular weight ofca. 2410 corresponding approximately to pentaerythritol 3.3PO+48EO. Theproduct remaining in the autoclave could be reacted on in a similarfashion to make other pentaerythritol alkoxylation products such aspentaerythritol 3.3PO+89EO, pentaerythritol 3.3PO+135EO andpentaerythritol 33PO+158EP.

[0092] Dodecenylsuccinic anhydride (18.1 g; 68 mmol) was added topentaerythritol 48-ethoxylate (81.9 g; 34 mmol), made as describedabove, in a 250 ml three necked flask equipped with a motor drivenpaddle stirrer, nitrogen line (providing an inert atmosphere) anddropping funnel, the reaction mixture was heated to and held at 100° C.for 6 hours to form the di-(dodecenylsuccinic acid)ester ofpentaerythritol 48-ethoxylate in a yield of 100 g, 100% theory. Thereaction was monitored using FT-IR and GLC. The C¹³ and H¹ NMR spectraof the ester product (without further purification) confirmed thestructure, indicating the absence of anhydride functionality and thatthe product was the substantially pure title ester.

[0093] SE1a—Di-(dodecenylsuccinic)ester of pentaeyrythritol48-ethoxylate

[0094] In a further simplified method the ethoxylated pentaerythritoland dodecenylsuccinic anhydride in a molar ratio of 1:2 were placed in asealed jar which was heated in an oven at about 100° C. for about 6hours. After this time the reaction was complete and the productessentially identical to that made in Example 1. For small scalepreparations of the compounds described below, this simplified methodwas generally used.

[0095] SE2-SE2O Further alkenylsuccinic esters of pentaerythritolethoxylates

[0096] The title compounds were made by the method described inSynthesis Example SE1, but varying the proportions of reagents andsubstituting the corresponding alkenyl succinic anhydride for thedodecenyl succinic anhydride used in SE1 to make the title compoundslisted below. As triglycerol is a liquid, it can be ethoxylated bydirect reaction with ethylene oxide under alkali catalysis withoutneeding to use the two stage technique used for pentaerythritol.

[0097] The products were all obtained in quantitative yield as liquidsor waxy solids. The identity of the products was confirmed by C¹³ and H¹NMR. The products of these Examples were (compounds where the value of mis non-integral are indicated as the x(non-integral)-(alkenyl succinicacid)ester):

[0098] SE2—3.9-(dodecenyisuccinic)ester of pentaerythritol 48-ethoxylate

[0099] SE3—di-(dodecenylsuccinic)ester of pentaerythritol 158-ethoxylate

[0100] SE4—3.9-(dodecenylsuccinic)ester of pentaerythritol15B-ethoxylate

[0101] SE5—di-(octadecenylsuccinic)ester of pentaerythritol48-ethoxylate

[0102] SE6—3.9-(octadecenylsuccinic)ester of pentaerythritol48-ethoxylate

[0103] SE7—di-(octadecenyisuccinic)ester of pentaerythritol158-ethoxylate

[0104] SE8—3.9-(octadecenylsuccinic)ester of pentaerythritol158-ethoxylate

[0105] SE9 tri-(tetradecenylsuccinic)ester of triglycerol 89-ethoxylate

[0106] SE10 4.9-(tetradecenyisuccinic)ester of triglycerol 89-ethoxylate

[0107] SE11 tri-(tetradecenylsuccinic)ester of triglycerol135-ebioxylate

[0108] SE12 4.9-(tetradecenylsuccinic)ester of tnglycerol 135-ethoxylate

[0109] SE13 tri-(tetradecenylsuccinic)ester of triglycerol169-ethoxylate

[0110] SE14 4.9-(tetradecenylsuccinic)ester of triglycerol169-ethoxylate

[0111] SE15 tri-(octadecenylsuccinic)ester of triglycerol 89-ethoxylate

[0112] SE16 4.9-(octadecenylsuccinic)ester of triglycerol 89-ethoxylate

[0113] SE17 tri-(octadecenylsuccinic)ester of triglycerol 135-ethoxylate

[0114] SE18 4.9-(octadecenylsuccinic)ester of triglycerol135-el,hoxylate

[0115] SE19 tri-(octadecenylsuccinic)ester of triglycerol 169-ethoxylate

[0116] SE20 4.9-(octadecenylsuccinic)ester of triglycerol 169-elhoxylate

[0117] SE21 2.9-(octadecenylsuccinic)ester of glycerol 120-ethoxylate

[0118] The title compound was made by the general method of SE1 butsubstituting glycerol 120-ethoxylate for the pentaerithritol-48ethoxylate and octadecenyl succinic anhydride for the dodecenyl succinicanhydride used in SE1 and changing the molar proportions of the reagentsto make the title compound. The intermediate glycerol 120-ethoxylate wasprepared by direct reaction of glycerol and ethylene oxide under alkalicatalysis; at about 120° C. The product was obtained as a waxy solid(melting at about 60° C.) in quantitative yield. The identity of theproduct was confirmed by C¹³ and H¹ NMR.

[0119] SE22 to SE29-(octadecenylsuccinc esters of sorbitol ethoxylates

[0120] The title compounds were made by the general method of SE1 butsubstituting sorbitol 80-ethoxylate and sorbitol 180-ethoxylate for thepentaerythritol ethoxylate and octadecenyl succinic anhydride for thedodecenyl succinic anhydride used in SE1 and changing the molarproportions of the reagents to make the title compounds. The productswere obtained as waxy solids in quantitative yield and their respectiveidentities confirmed by C¹³ and H¹ NMR. The products of these Exampleswere:

[0121] SE22 tri-(octadecenylsuccinic)ester of sorbitol 90-ethoxylate

[0122] SE23 hexa-(octadecenylsuccinic)ester of sorbitol 90-ethoxylate

[0123] SE24 tri-(octadecenyisuccinic)ester of sorbitol 180-ethoxylate

[0124] SE25 hexa-(octadecenylsuccinic)ester of sorbitol 180-ethoxylate

[0125] SE26 tri-(octadecenyisuccinic)ester of sorbitol 130-etho)ylate

[0126] SE27 hexa-(octadecenyisuccinic)ester of sorbitol 130-ethoxylate

[0127] SE28 tri-(octadecenylsuccinic)ester of sorbitol 220-etho)ylate

[0128] SE29 hexa-(octadecenylsuccinic)ester of sorbitol 220-ethoxylate

[0129] In practice, in these Examples, water was used to dissolve thesorbitol prior to ethoxylation so that the ethoxylates were mixtures ofthe respective sorbitol ethoxylates and polyoxyethylene glycol (PEG).The levels of ethoxylation indicated represent the total amount ofethylene oxide consumed in the ethoxylation based on the sorbitol used.Accordingly the ester products are in, effect, a mixture of the sorbitolethoxylate succinic tri- or hexa-ester and the corresponding PEGsuccinic diester.

[0130] SE30 to SE35—Various esters of ethylene diamine PO/EO Blockpolyalkoxylate

[0131] The title compounds were made by the general method of SE21 butsubstituting ethylene diamine PO/EO (94/90) block polyalkoxylate for theglycerol ethoxylate and the appropriate alkenyl succinic anhydride forthe dodecenyl succinic anhydride used in SE21 and changing the molarproportions of the reagents to make the title compounds. Theintermediate block polyalkoxylate was made by reacting ethylene diaminetetrapropoxylate (1 PO unit condensed onto each amino active hydrogen)with propylene oxide using KOH as catalyst at about 125° C. to make the94 mole PO condensate and subsequently feeding ethylene oxide to thereaction mix for at ime and in an amount to make the blockpolyalkoxylate. The title products were obtained as waxy solids inquantitative yield (based on the alkoxylates) and their respectiveidentities confirmed by C¹³ and H¹ NMR. The products of these Exampleswere:

[0132] SE30 3.9-(octadecenylsuccinic)ester of ethylene diamine PO/EO(94/90) block polyalkoxylate

[0133] SE31 3.9-(octadecenylsuccinic)ester of ethylene diamine POIEO(94/140) block polyalkoxylate

[0134] SE32 3.9-(octadecenyisuccinic)ester of ethylene diamine PO/EO(94/180) block polyalkoxylate

[0135] SE33 3.9-(hexadecenyisuccinic)ester of ethylene diamine POIEO(94/90) block polyalkoxylate

[0136] SE34 3.9-(hexadecenylsuccinic)ester of ethylene diami'le POIEO(94/140) block polyalkoxylate

[0137] SE35 3.9-(hexadecenylsuccinic)ester of ethylene diamine POIEO(94/180) block Polyalkoxylate

[0138] SE36-SE39 Various alkenyl succinic esters of glycerol ethoxylates

[0139] The title compounds were made by the general method described inExample SE1 above but using appropriate glycerol ethoxylates for thepentaerithritol-48 ethoxylate used in SE1 and the appropriate alkenylsuccinic anhydrides and adjusting the molar proportions of the reagentsto make the title compounds. The intermediate glycerol ethoxylates wereprepared by direct reaction of glycerol and ethylene oxide under alkalicatalysis at about 120° C. The products were obtained as waxy solids(melting at about 60° C.) in quantitative yield and their identity wasconfirmed by C¹³ and H¹ NMR.

[0140] The title compounds of these Examples are:

[0141] SE36 2.9-(dodecenylsuccinic)ester of glycerol 44-ethoxylate

[0142] SE37 2.9-(dodecenyisuccinic)ester of glycerol 61-ethoxylate

[0143] SE38 2.9-(tetradecenyisuccinic)ester of glycerol 61-ethoxytate

[0144] SE39 2.9-(octadecenylsuccinic)ester of glycerol 61-ethoxylate

[0145] SE40 and SE41 alkenylsuccinic diesters of polyethylene glycol

[0146] The title compounds were made by the general method of ExampleSE1 but using polyethylene glycol (PEG) having a stated averagemolecular weight instead of the pentaerithritol-48 ethoxylate used inSE1 and using octadecenyl succinic anhydride instead of the dodecenylsuccinic anhydride used in SE1 and adjusting the molar proportions toobtain the desired title compound. The products were all obtained inquantitative yield as liquids or waxy solids. The identity of theproducts was confirmed by C¹³ and H¹ NMR.

[0147] SE40 dioctadecenylsuccinic ester of PEG 4500

[0148] SE41 dioctadecenylsuccinic ester of PEG 5000

APPLICATION EXAMPLES AE1 to AE9

[0149] A base shampoo was made up having the following composition:Material Parts by weight Tween 20 10.0 Miranol C2M 13.2 Steol CS-33017.2 deionized water 57.0 Dowcil 200 0.1 Total 97.5

[0150] The pH of this base was adjusted to between 7 and 7.5. To thisbase was added 2.5 parts by weight of thickener and then the pH of thatmixture was adjusted to between 6 and 7 with 50% aqueous citric acid.The test samples were stored for 24 hours (at least) in a 25° C. waterbath. Viscosity measurements were then taken using a Brookfield ModelLVDV1 viscometer. The thickeners for AE1 to AE9 were selected from thoseof SE1 to SE8 and SE21. A comparative Example AEC1 was included using2.5 parts by PEG distearate (mean of 3 tests). The structures of thethickeners and the results of viscosity testing are set out in Table A1below. TABLE A1 Thickener Viscosity AE No SE No ASA ester no core EO no(mPa · s) AEC1 — — — — — 175 AE1 SE1 C12 2 PE 48 13.7 AE2 SE2 C12 3.9 PE48 199.2 AE3 SE3 C12 2 PE 158 158 AE4 SE4 C12 3.9 PE 158 21 AE5 SE5 C182 PE 48 13.5 AE6 SE6 C18 3.9 PE 48 19.7 AE7 SE7 C18 2 PE 158 116 AE8 SE8C18 3.9 PE 158 12700 AE9 SE21 C18 2.9 glycerol 120 66.0

APPLICATION EXAMPLES AE10 to AE21

[0151] A further set of alkenyl succinic esters of ethoxylatedtriglycerol thickeners was tested as described for Application ExampleAE1 above. The structures of the thickeners and the viscosity resultsare set out in Table A2 below. TABLE A2 Thickener Viscosity AE No SE NoASA ester No core EO No (mPa · s) AE10 SE9 C14 3 tri-gly 89 58.9 AE11SE10 C14 4.9 tri-gly 89 89.2 AE12 SE11 C14 3 tri-gly 135 744 AE13 SE12C14 4.9 tri-gly 135 288.6 AE14 SE13 C14 3 tri-gly 169 39.3 AE15 SE14 C144.9 tri-gly 169 357 AE16 SE15 C18 3 tri-gly 89 99.9 AE17 SE16 C18 4.9tri-gly 89 4180 AE18 SE17 C18 3 tn-gly 135 52 AE19 SE18 C18 4.9 tri-gly135 2468 AE20 SE19 C18 3 tri-gly 169 67.6 AE21 SE20 C18 4.9 tri-gly 1693402

APPLICATION EXAMPLES AE22 to AE29

[0152] A set of alkenyl succinic esters of sorbitol ethoxylates wastested as thickeners as described for Application Examples AE1 to AE9above. The structures of the thickeners and viscosity results are setout in Table A3 below. TABLE A3 Thickener Viscosity AE No SE No ASAester No EO No (mPa · s) AE22 SE22 18 3 90 23 AE23 SE23 18 6 90 94.5AE24 SE24 18 3 180 29.7 AE25 SE25 18 6 180 257 AE26 SE26 18 3 130 34AE27 SE27 18 6 130 554 AE28 SE28 18 3 220 40 AE29 SE29 18 6 220 1198

APPLICATION EXAMPLES AE30 to AE35

[0153] A set of alkenyl succinic esters of ethylene diamine alkoxylateswas tested as thickeners as described for Application Examples AE1 toAE9 above. The structures of the thickeners and the viscosity resultsare set out in Table A4 below. TABLE A4 Thickener Viscosity AE No SE NoASA ester No core PO No EO No (mPa · s) AE30 SE30 C18 3.9 eth 94 90 19.6diam AE31 SE31 C18 3.9 eth 94 140 105.3 diam AE32 SE32 C18 3.9 eth 94180 86.6 diam AE33 SE33 C16 3.9 eth 94 90 379 diam AE30a SE30 C18 3.9eth 94 90 1115 diam AE34 SE34 C16 3.9 eth 94 140 1265 diam AE31a SE31C18 3.9 eth 94 140 3960 diam AE35 SE35 C16 3.9 eth 94 180 1503 diamAE32a SE32 C18 3.9 eth 94 180 3230 diam

APPLICATION EXAMPLES AE36 to AE40

[0154] The thickening properties of compounds of the invention inaqueous formulation were compared with conventional amine oxidesurfactant thickeners. The formulations tested included varying amountsof sodium chloride to asses the effect of low to moderate electrolyteconcentrations on the thickening properties of the materials. The basicformulation used was as follows: Material Parts by weight SLES 15thickener  4.5 salt variable  0, 1 or 2 water 80.5

[0155] A similar comparison formulation was made up as AEC2 butcontaining 15 parts of CDMO and 66 parts of water. The structures of thethickeners amounts, of salt used and the results of viscosity testingare set out in Table A6 below. TABLE A6 Viscosity (mPa · s) Thickenersalt amount (g) AE No SE No ASA C No ester No Core EO No 0 1 2 AEC2 — —— — — 12 150 320 AE36 SE18 C18 4.9 tri-gly 135 10200 3400 216000 AE37SE20 C18 4.9 tri-gly 169 252000 — — AE38 SE14 C14 4.9 tri-gly 169 32006000 6400 AE39 SE2 C12 3.9 PE 48 40 20 40 AE40 SE4 C12 3.9 PE 158 840 **

APPLICATION EXAMPLES AE41 to AE47

[0156] Various compounds of the invention were tested for their abilityto disperse titanium dioxide pigment in an aqueous formulation. Thepigment formulation had the following composition: Material Parts byweight TR92 65 water 35 dispersant 1.5

[0157] The viscosity of the pigment dispersions was measured using aBrookfield LVT viscometer at 6 rpm (0.1 Hz). The results are set out inTable A7 below. TABLE A7 Dispersant Viscosity AE No SE No ASA C No esterNo Core EO No (mPa · s) AE41 SE36 C12 2.9 glycerol 44 100 AE42 SE37 C122.9 glycerol 61 49 AE43 SE38 C14 2.9 glycerol 61 12 AE44 SE39 C18 2.9glycerol 61 12

APPLICATION EXAMPLES TO AE45 to AE47

[0158] Various diesters of PEG were tested as thickeners in shampooformulations. The formulations tested were based on a mild shampoo baseand comparison runs were made using a shampoo made by thickening theshampoo base with 0.5% by weight of PEG 6000 distearate (AEC3) and witha commercially available proprietary shampoo using a similar shampoobase thickened with PEG distearate (AEC4). The viscosity of thethickened shampoos was measured at various shear rates in the range 10to 100 s⁻¹. The materials used are set out in Table A8a, the measuredviscosities of the formulations in Table A8b and the viscosities as apercentage of the measured viscosity at a shear rate of 10 s⁻¹ are setout in Table 8c below. These data indicate that the compounds of andused in this invention give higher viscosities at comparable levels ofaddition and exhibit desirably greater shear thinning that theconventional thickener (PEG 6000 distearate). Table A8a Thickener Amount(wt % on AE No SE No ASA C No ester No Core shampoo base) AEC3 PEGdistearate 0.5 AEC4 PEG distearate (not known) AE45 SE40 C18 2 PEG 45000.5 AE46 SE41 C18 2 PEG 5000 1 AE47 SE41 C18 2 PEG 5000 2.5

[0159] TABLE A8b Viscosity (m.Pa · s) Shear rate (s⁻¹) AE No 10 20 30 4050 60 70 80 90 100 AEC3 2310 2286 2236 2162 2117 2047 2007 1943 18641817 AEC4 877.9 868.1 850 8749.1 845.3 820.7 811 802.9 800.8 791.1 AE483558 3526 3417 3251 3077 2908 2767 2602 2505 2398 AE49 3960 3345 32343133 2972 2789 2684 2537 2432 2324 AE50 4242 3982 3867 3738 3569 34453310 3188 3100 3013

[0160] Table A8c Viscosity as a percentage low shear viscosity Shearrate (s⁻¹) AE No 10 20 30 40 50 60 70 80 90 100 AEC3 100 99 96.8 93.691.6 88.6 86.9 84.1 80.7 78.7 AEC4 100 98.9 96.8 96.7 96.3 93.5 92.491.5 91.2 90.1 AE48 100 98.3 95.2 90.6 85.8 81 77.1 72.5 69.8 66.8 AE49100 84.5 81.7 79.1 75.1 70.4 67.8 64.1 61.4 58.7 AE50 100 93.9 91.2 88.184.1 81.2 78 75.2 73.1 71

APPLICATION EXAMPLE AE48

[0161] Shampoo base/showergel type compositions were made up usingvarious thickeners in the following formulation: Material Parts byweight Arlatone 1489 10 Tensiomild HM 20 Tengobetain L7 10 Germaben II 2Thickener 2 Water to 100

[0162] The thickener of SE7 was compared with G 1821 a commerciallyavailable PEG 6000 distearate and a commercially available proprietarytetrastearate thickener. The results are given in Table A9 below. TABLEA9 Dispersant Viscosity AE No SE No ASA C No ester No Core EO No (mPa ·s) AEC5 G 1821 (PEG 6000 distearate) 200 AEC6 Crothix (pentaerythritolethoxylate tetrastearate) 35000 AE48 SE7 18 3.9 PE 158 65000

What is claimed is:
 1. Compounds of the formula (I):R².[(AO)_(n).R³]_(m)   (I) where: R² is the residue of a group having atleast m active hydrogen atoms derived from hydroxyl and/or amino and/oramido groups; AO is an alkylene oxide residue, which may vary along thechain; each n is from 2 to 200; m is from 2 to 10; and each R³ is H,hydrocarbyl, long chain alk(en)yl succinic acyl group of the formulaOC.(HR)C.C(HR¹).COY where: one of R and R¹ in the succinic moiety is C₈to C₂₂ alkenyl or alkyl and the other is hydrogen, and Y is a group OMwhere M is hydrogen, metal, amonium, amine, especially alkylamine(including alkanolamine), onium, hydrocarbyl; or Y is NR⁴R⁵ where R⁴ andR⁵ are each independently hydrogen, hydrocarbyl, particularly alkyl; ora long chain acyl group —OC.R⁶, where R⁶ is a long chain hydrocarbylgroup; or a short chain acyl group —OC.R⁷, where R⁷ is a short chainhydrocarbyl group; where at least two of the groups R³ are long chainacyl groups, and at least one of the long chain acyl groups is/are longchain alkenyl or alkyl succinic group(s); provided that where R¹ isethylene glycolyl or propylene glycolyl, m is 2, and both groups R² arealk(en)yl succinic groups, the total of the indices n is at least 120.2. Compounds of the formula (Ia): R².[(AO)_(n).R³]_(m)   (Ia) where: R²is the residue of a group having at least m active hydrogen atomsderived from hydroxyl and/or amino and/or amido groups; AO representsethylene oxide residues or a mixture of ethylene oxide residues andpropylene oxide residues in which the molar proportion of ethylene oxideresidues is at least 50% and desirably at least 70%; each n is from 10to 200 such that the total of the indices n is at least 120 m is from 2to 10; each R³ is H; hydrocarbyl; a long chain alk(en)yl succinic acylgroup of the formula: —OC.(HR)C.C(HR¹).COY where: one of R and R¹ in thesuccinic moiety is C₈ to C₂₂ alkenyl or alkyl and the other is hydrogen,and Y is a group OM where M is hydrogen, metal, amonium, amine, or Y isNR⁴R⁵ where R⁴ and R⁵ are each independently hydrogen, a hydrocarbylgroup; a long chain acyl group —OC.R⁶, where R⁶ is a long chainhydrocarbyl group; or a short chain acyl group —OC.R⁷, where R⁷ is ashort chain hydrocarbyl group; where at least two of the groups R³ arelong chain acyl groups and at least one of the long chain acyl groupsis/are long chain alkenyl or alkyl succinic group(s).
 3. A compound asclaimed in either claim 1 or claim 2 in which at least two of the groupsR³ are long chain acyl groups and at least two of the long chain acylgroups is/are long chain alkenyl or alkyl succinic group(s).
 4. Acompound as claimed in claim 3 where at least three of the groups R³ arelong chain acyl groups and at least three of the long chain acyl groupsis/are long chain alkenyl or alkyl succinic group(s).
 5. A compound asclaimed in any one of claims 1 to 4 wherein, when R³ is hydrocarbyl itis a C₁ to C₂₂ alkyl or alkenyl group and when R³ is a long chainalk(en)yl succinic acyl group one of R⁴ and R⁵ is polyhydroxysubstituted alkyl group.
 6. A compound as claimed in claim 5 wherein oneof R⁴ and R⁵ is an open chain tetratol, pentitol, hexitol or heptitolgroup or an anhydro derivative of such a group.
 7. A compound as claimedin claim 5 wherein one of R⁴ and R⁵ is a residue of, or a residuederived from, glucose, fructose, maltose or palitose.
 8. A compound asclaimed in any one of claims 1 to 7 wherein the group R² is a residue ofglycerol or a polyglycerol; a tri- or higher polymethylol alkane; asugar, an etherifierd sugar; a partial alkyl ethers of a sugar; an etheroligo-/poly-mers of a sugar; a sugar ester; a polyhydroxy carboxylicacid; an amine; an amino-alcohol; a carboxylic acid amide; or an amidocarboxylic acid.
 9. A compound as claimed in claim 8 wherein the groupR² is a residue of glycerol, diglycerol, triglycerol, trimethylolethane, trimethylol propane, penterythritol, sorbitol, mannitol,sorbitan, methyl glucose, a dextrin, lauric, palmitic, oleic, stearic orbehenic acid esters of sorbitan or a sorbitols, citric acid, tartaricacid, ethylene diamine 2-aminoethanol, di-ethanolamine, triethanolamine,urea, malonamide, succinamide, or succinamic acid.
 10. A compound asclaimed in any one of claims 1 to 9 wherein m is from 3 to
 6. 11. Amethod of thickening an aqueous system which comprises including in theaqueous phase a thickening effective amount of a compound of the formula(II): R¹².[(AO²)_(n2).R¹³]_(m2)   (II) where: R¹² is the residue of anoptionally substituted hydrocarbyl group having at least m activehydrogen atoms derived from hydroxyl and/or amino and/or amido groups;AO² is an alkylene oxide residue, which may vary along the chain; eachn2 is from 10 to 200, such that the total of the indices n2 is at least50; m2 is from 2 to 10; and each R¹³ is H, hydrocarbyl, a long chainalk(en)yl succinic acyl group of the formula: —OC.(HR¹⁰)C.C(HR¹¹).COY²where: one of R¹⁰ and R¹¹ in the succinic acid moiety is C₈ to C₂₂alkenyl or alkyl and the other is hydrogen, and Y² is a group OM² whereM² is hydrogen, metal, amonium, amine especially alkylamine, alkyl; orY² is NR¹⁴R¹⁵ where R¹⁵ and R¹⁵ are each independently hydrogen, ahydrocarbyl; or a long chain acyl group —OC.R¹⁶, where R¹⁶ is a longchain hydrocarbyl group; or a short chain acyl group —OC.R¹⁷, where R¹⁷is a short chain hydrocarbyl group; where at least two of the groups R¹³are long chain acyl groups, and at least one of the long chain acylgroups is a long chain alkenyl or alkyl succinic group.
 12. A method asclaimed in claim 9 wherein the compound of the formula (II) is acompound of the formula (I) or (Ia) as defined in any one of claims 1 to7.
 13. A method as claimed in claim 10 wherein the aqueous system is anoil-in-water emulsion, a water-in-oil emulsion, an aqueous solution or adispersions of solids in an aqueous system.